CN114158568B - Composite antibacterial agent and preparation method and application thereof - Google Patents
Composite antibacterial agent and preparation method and application thereof Download PDFInfo
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
- A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
- A01N43/14—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
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- C07D471/12—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains three hetero rings
- C07D471/14—Ortho-condensed systems
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- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C1/00—Chemical treatment prior to tanning
- C14C1/08—Deliming; Bating; Pickling; Degreasing
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- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C3/00—Tanning; Compositions for tanning
- C14C3/02—Chemical tanning
- C14C3/08—Chemical tanning by organic agents
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- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C3/00—Tanning; Compositions for tanning
- C14C3/02—Chemical tanning
- C14C3/08—Chemical tanning by organic agents
- C14C3/22—Chemical tanning by organic agents using polymerisation products
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- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C9/00—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes
- C14C9/02—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes using fatty or oily materials, e.g. fat liquoring
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Abstract
The application discloses a composite antibacterial agent, a preparation method and application thereof, wherein the composite antibacterial agent comprises the following components: uniformly mixing polyphosphoric acid, diethylene glycol dimethyl ether, thionyl chloride and phosphoric acid to obtain a catalyst solution; taking a catalyst solution, adding a salified compound, uniformly mixing, adding gluconic acid, uniformly mixing, adding polyphosphoric acid, reacting for a period of time, adding gluconic acid, reacting for a period of time, cooling to 45-50 ℃, and adding water to obtain the glucopyrido-bisimidazole; and thirdly, uniformly mixing chitosan oligosaccharide, gluco-pyrido-dipyridyl-bisimidazole, water, acetic acid and zinc chloride, then adding triethylamine, and reacting for a period of time to obtain the zinc oxide-chitosan oligosaccharide/gluco-pyrido-dipyridyl-bisimidazole composite antibacterial agent. The leather of the application does not contain heavy metals and hexavalent chromium which pollute the environment and cause harm to human bodies, the free formaldehyde content accords with the restriction standard of European Union on formaldehyde in leather which is directly contacted with the skin, and meanwhile, the leather has excellent antibacterial performance.
Description
Technical Field
The application relates to the technical field of tanning, in particular to a composite antibacterial agent and a preparation method and application thereof.
Background
Leather has elegant color, natural lines, fine hand feeling and comfortable wearing, has absolute advantages in the market, and has long been used as an important raw material in the fields of high-grade shoes, luggage, leisure products, furniture decoration and the like. Leather belongs to collagen-based high polymer materials, leather products cannot be washed frequently, particularly footwear products, sweat or dirt residues are easily caused by simply wiping and airing, and under proper temperature and humidity conditions, a plurality of harmful microorganisms such as bacteria and viruses are easily bred, so that the quality of the leather products is seriously affected, and meanwhile, the physical health of human beings is also seriously threatened.
In the conventional leather making process, special antibacterial procedures are hardly available, and the aim of inhibiting leather from mildewing is fulfilled mainly by adding the mildew inhibitor in the leather making production process, but the mildew inhibitor has the problems of easiness in generating drug resistance, high cost, poor permeability, high toxicity, environmental pollution and the like. In addition, the addition of the antibacterial agent in the manufacturing process of the leather product at the later stage can ensure that the leather product has a certain antibacterial self-cleaning capability, but the antibacterial durability is poor. Therefore, in order to impart durable and efficient antimicrobial properties to leather and leather products, it is also necessary to start from the tanning process.
Disclosure of Invention
The embodiment of the application solves the technical problem of weak antibacterial capability of leather in the prior art by providing the composite antibacterial agent, the preparation method and the application thereof, and realizes the leather which does not contain heavy metals and hexavalent chromium causing pollution to the environment and harm to human bodies, and the free formaldehyde content accords with the restriction standard of European Union on formaldehyde in leather directly contacted with the skin, meanwhile, the leather has excellent antibacterial performance, and the product has full and bright color, soft and plump leather body and uniform grains.
The embodiment of the application provides a preparation method of a composite antibacterial agent, which comprises the following steps:
step (1): uniformly stirring and mixing 10-15 parts of polyphosphoric acid, 30-40 parts of diethylene glycol dimethyl ether, 5-10 parts of thionyl chloride and 50-80 parts of phosphoric acid at 90-110 ℃ to obtain a catalyst solution;
step (II): taking 25-35 parts of catalyst solution, adding 50-80 parts of salicide, stirring and mixing uniformly at 50-80 ℃, then adding 100-160 parts of gluconic acid, mixing uniformly, adding 1-3 parts of polyphosphoric acid, reacting for a period of time at 90-110 ℃, adding 10-16 parts of gluconic acid, heating to 175-185 ℃ for reacting for a period of time, cooling to 45-50 ℃, and adding 200-500 parts of water to obtain the bipyridyl bisimidazole gluconate;
step (III): mixing 95-105 parts of chitosan oligosaccharide, 30-50 parts of gluco-pyrido-pyridine bisimidazole, 200-500 parts of water, 5-10 parts of acetic acid and 10-15 parts of zinc chloride uniformly, adding 15-20 parts of triethylamine, and reacting for a period of time at 30-50 ℃ to obtain the zinc oxide-chitosan oligosaccharide/gluco-pyrido-pyridine bisimidazole composite antibacterial agent.
The hydrochloride is 2,3,5, 6-tetraminopyridine hydrochloride or sulfate.
The structural formula of the glucodipyridyl bisimidazole is as follows:
a composite antibacterial agent is prepared by the method disclosed by the application.
The preparation method of the metal-free tanning antibacterial ecological leather at least comprises the following steps:
softening, neutralizing, washing, filling, fatting, sterilizing, washing, drying and finishing, and adding the zinc oxide-chitosan oligosaccharide/gluco-pyridine bisimidazole compound antibacterial agent in the antibacterial procedure.
Further, the fatting procedure and the filling procedure are carried out in the same bath, and the specific steps are as follows: adding 120-200% hot water, 2.0-5.0% high concentration solvent type grease, 5.0-10.0% synthetic soft grease into the bath liquid, and rotating at 50-53 ℃.
Further, the antibacterial procedure and the filling and fatting procedures are carried out in the same bath, and the specific steps are as follows: adding 2-10% zinc oxide-chitosan oligosaccharide/glucodipyridyl bisimidazole compound antibacterial agent into the bath liquid, rotating, adding 2.5-3.0% formic acid for 3 times, rotating, and regulating pH of the bath liquid to 3.2-3.6.
Further, the specific steps of the softening process are as follows: adding 200-300% water, 0.5-3.0% multifunctional rewetting agent and 0.1-0.3% nonionic degreasing agent into the rotary drum, and rotating at 45-53 ℃.
Further, the neutralization process and the softening process are carried out in the same bath, and the specific steps are as follows: adding 1.0-5.0% synthetic tanning auxiliary agent into the bath liquid, rotating, and regulating pH of the bath liquid to 3.8-4.3.
Further, the specific steps of the filling procedure are as follows: adding 30-80% water, 1.0-3.0% synthetic tanning auxiliary agent, 1.5-5.0% silicon fatting agent, 1.5-6.0% polymer fatting agent and 1.5-3.0% nonionic fatting agent into a rotary drum, and rotating at 30-35 ℃; adding 5.0-8.0% sulfone synthetic tanning agent, 5.0-8.0% sulfone-phenol copolymer synthetic tanning agent, 1.0-4.0% dispersed tannin, and rotating; adding 1.5-5.0% of silicon fatliquoring agent, 1.5-6.0% of polymer fatliquoring agent, 1.5-3.0% of nonionic fatliquoring agent, 2.0-5.0% of sulfone synthetic tanning agent, 8.0-11.0% of sulfone-phenol copolymer synthetic tanning agent and 1.0-4.0% of dispersed tannin, and rotating; adding 8.0-15.0% of compound synthetic tanning agent, 2.0-6.0% of acrylic acid polymer tanning agent and 3.0-8.0% of melamine resin tanning agent, and rotating.
One or more technical solutions provided in the embodiments of the present application at least have the following technical effects or advantages:
1. the synthesis principle of the gluco-pyrido bisimidazole is that 1mol of carboxyl and 2mol of amino are condensed under the catalysis of polyphosphoric acid, and when 2 molecular amino groups are adjacent positions, the generated structure is an imidazole structure. The gluco-pyrido bisimidazole contains a large number of hydroxyl and imino active functional groups, and can be well associated with amino groups and hydroxyl groups on chitosan oligosaccharide by hydrogen bonds, so that entanglement is formed. The gluco-pyridine bisimidazole exhibits weak cationic property, can well neutralize the strong cationic property of chitosan, and can well solve a plurality of problems caused by the strong cationic property of chitosan oligosaccharide (for example, because of the strong cationic property, the shellOligosaccharide is easy to co-precipitate with other retanning filling materials, and the usability is affected; and chitosan oligosaccharide needs to be used at a lower pH value, and the pH value is usually higher than 3.5 when retanning is filled. In addition, the gluco-pyridine bisimidazole can also destroy a hydrogen bond network formed by the chitosan oligosaccharide (the molecular structure of the chitosan oligosaccharide is easy to generate intramolecular hydrogen bond crosslinking, so that the particle size of the chitosan oligosaccharide is increased, the chitosan oligosaccharide is difficult to enter the collagen fiber, and the chitosan oligosaccharide is easy to separate when coprecipitated with zinc chloride due to high intramolecular hydrogen bond crosslinking degree, so that the zinc chloride cannot be adsorbed on the chitosan oligosaccharide molecule). In addition, the gluco-dipyridyl bisimidazole can also improve the compatibility of chitosan oligosaccharides with many conventional retanning filling materials, such as: the aromatic ring structure of the tannin extract, the synthetic tannin and the dye is the same as that of the tannin extract, the synthetic tannin and the dye, and pi-pi interaction can be formed between the aromatic ring structure and the tannin extract, the synthetic tannin and the dye, so that the absorption of the tannin extract, the synthetic tannin and the dye is promoted; the acrylic resin has similar flexible chain segments, and the polyhydroxy chain segments of the gluconic acid can form a hydrogen bond network with the acrylic resin, so that the penetration of the acrylic resin among the skin collagen fibers is improved; the chitosan oligosaccharide and the gluco-pyridine bisimidazole have rich hydroxyl groups, and can promote the composite material and the inorganic filler (such as superfine kaolin and nano TiO) for leather making and filling 2 Meanwhile, a certain amount of inorganic filler is arranged in the protein filler and the amino resin), so that the utilization rate of the inorganic filler for leather making filling is improved, the combination of the leather collagen fiber and the inorganic filler is promoted, and the like. In addition, the gluco-pyridine bisimidazole can also reduce the viscosity of chitosan oligosaccharide, thereby improving the adsorption capacity of the collagen fiber to the chitosan oligosaccharide.
2. Common bacteria in leather include staphylococcus aureus, klebsiella pneumoniae and candida albicans, and the composite antibacterial agent has good killing and inhibiting effects on the three bacteria. The specific antibacterial principle is as follows: cations of chitosan oligosaccharide and Mg in bacterial cell wall existing in leather 2+ And Ca 2+ Ion competition, binding to the polyanion on the cell surface, causing the cell wall to lose integrity, K + Leakage from the cytoplasm, and cell death by contact with zinc oxide. K (K) + After leakage, RNA andprotein release, and rapid bacterial death after the bacteria have deleted RNA and protein. The chitosan oligosaccharide can also be used as a chelating agent to selectively bind trace metals, thereby inhibiting the generation of toxins and the growth of microorganisms. At the same time, chitosan oligosaccharides also activate defensive processes in host tissues, act as water binding agents and inhibit enzyme production. Chitosan oligosaccharides also penetrate the cell membrane of microorganisms and interfere with the synthesis of RNA and proteins. In addition, after the bacteria are contacted with zinc oxide, the bacterial permeability is increased due to the leakage of o-nitrophenol, beta-D-galactoside and other molecules in the bacteria.
3. The leather collagen fiber exists in a porous net form and contains a plurality of polar groups (such as carboxyl, amino, hydroxyl, imino and the like), thereby laying a foundation for the combination of antibacterial materials. The collagen fiber is amphoteric and anionic, and the chitosan oligosaccharide-zinc oxide/glucodipyridyl bisimidazole is weak cationic, so that the chitosan oligosaccharide-zinc oxide/glucodipyridyl bisimidazole has better combination capability from the aspect of electric charge. From the angle analysis of functional groups, amino groups of the composite material can be in hydrogen bond association with carboxyl groups and hydroxyl groups on the collagen fibers, rich hydroxyl groups on the composite material can be in hydrogen bond association with the carboxyl groups, the hydroxyl groups and the amino groups on the collagen fibers, and meanwhile, a special aromatic ring structure of the composite material can be in pi-pi interaction association with special amino acids (such as phenylalanine) on the collagen fibers, so that the chitosan oligosaccharide-zinc oxide/glucopyridopyridine bisimidazole has excellent compatibility with the collagen fibers.
4. The composite antibacterial agent is prepared by compounding inorganic materials, organic materials and hydrophilic substances, has good water solubility and dispersion stability, is applied to the wet dyeing and finishing section of ecological leather, and expands the application field of the antibacterial agent. Meanwhile, the composite antibacterial agent has high-efficiency, broad-spectrum and durable antibacterial activity, can show excellent antibacterial effect with less dosage, does not greatly increase the tanning production cost, and is safe and nontoxic to human bodies; the composite antibacterial agent is firmly combined with the collagen fibers through chemical bond or adsorption, so that the defects of poor compatibility, water washing intolerance, low safety and the like of the traditional leather mildew preventive and leather base materials are overcome;
5. the leather preparation method of the application does not contain heavy metals and hexavalent chromium which pollute the environment and cause harm to human bodies, and the free formaldehyde content accords with the restriction standard of European Union on formaldehyde in leather which is directly contacted with the skin; on the other hand, the ecological leather is endowed with excellent antibacterial property, the service performance is improved, the product is full and bright in color, the leather body is soft and plump, and the lines are uniform.
Detailed Description
In order to better understand the above technical solution, the following description will be given in detail with reference to the specification and the specific embodiments (the chemical materials are used in amounts based on the weight of the wet blue leather, for example 100kg of wet blue leather, 200% water is 200kg water).
Example 1
The preparation method of the metal-free tanning antibacterial ecological leather at least comprises the following steps:
the step (a) of preparing a composite antibacterial agent comprises the following steps:
step one, uniformly mixing 10 parts of polyphosphoric acid, 30 parts of diethylene glycol dimethyl ether, 5 parts of thionyl chloride and 50 parts of phosphoric acid at 100 ℃ for 2 hours to obtain a catalyst solution;
step two, taking 30 parts of catalyst solution, adding 50 parts of 2,3,5, 6-tetraminopyridine hydrochloride, stirring at 50 ℃ for 12 hours, uniformly mixing, then adding 100 parts of gluconic acid, adding 1 part of polyphosphoric acid after uniformly mixing, reacting at 100 ℃ for 6 hours, adding 10 parts of gluconic acid, and heating to 180 ℃ for reacting for 0.5 hour. Cooling to 50 ℃, and adding 200 parts of water to obtain the gluco-pyrido-bisimidazole;
and step three, taking 100 parts of chitosan oligosaccharide, 30 parts of gluco-pyrido-pyridine bisimidazole, 200 parts of water, 5 parts of acetic acid and 10 parts of zinc chloride, uniformly mixing, then adding 15 parts of triethylamine, and reacting for 4 hours at 30 ℃ to obtain the zinc oxide-chitosan oligosaccharide/gluco-pyrido-pyridine bisimidazole composite antibacterial agent.
Step (b) is soft: 200% of water, 0.5% of multifunctional rewetting agent PELLAN GLH (German Kekai chemical company) and 0.1% of nonionic degreasing agent Euscapon OC (Stta Co.) are added into the rotary drum, and the rotary drum is rotated for 30min at the temperature of 53 ℃;
step (c) neutralization: adding 1.0% of synthetic tanning auxiliary Tamol X NL (Stoul company) into the bath, rotating for 60min, and regulating the pH of the bath to 3.8;
step (d) conventional water washing;
filling in the step (e): 30% water, 1.0% synthetic tanning auxiliary agent Tamol X NL (Stokes Co.), 1.5% silicon fatting agent Densmodrin CD (Stokes Co.), 1.5% polymer fatting agent Stahlite AL3 (Stokes Co.), 1.5% nonionic fatting agent AMIDOIL PLUS (Spanish Sha Bei Gongsi) are added to the drum, the temperature is 30 ℃, and the drum is rotated for 30 minutes; 5.0% of sulfone synthetic tanning agent Tanicor SXP (Stokes corporation), 5.0% of sulfone-phenol copolymer synthetic tanning agent Basyntan MLB (Stokes corporation) and 1.0% of dispersed tannin Tamol M (Stokes corporation) are added, and the mixture is rotated for 60 minutes; the rotation is carried out for 150min by adding 1.5% of a silicon fatting agent Denscorin CD (Style company), 1.5% of a polymer fatting agent Stahlite AL3 (Style company), 1.5% of a nonionic fatting agent AMIDOIL PLUS (Spanish Sha Bei Gongsi), 2.0% of a sulfone synthetic tanning agent Tanicor SXP (Style company), 8.0% of a sulfone-phenol copolymer synthetic tanning agent Basyntan MLB (Style company), 1.0% of dispersed tannin Tamol M (Style company); adding 8.0% of composite synthetic tanning agent Basyntan X HL (Stokes company), 2.0% of acrylic polymer tanning agent TERGOTAN PMB (Stokes company) and 3.0% of melamine resin tanning agent RELUGAN DLF (Stokes company), and rotating for 60min;
and (f) fatting: adding 120% of hot water at 60deg.C, 2.0% of high concentration solvent oil AS-723 (Scoll company), 5.0% of synthetic soft oil PELLASTOL 94S (Sema chemical company), and rotating at 50deg.C for 60min;
step (g) antibacterial: adding 2.0% zinc oxide-chitosan oligosaccharide/gluco-pyridine bisimidazole compound antibacterial agent into the bath liquid, rotating for 60min, adding 2.5% formic acid for 3 times, rotating for 30min each time, and regulating pH of the bath liquid to 3.6;
step (h) conventional water washing;
and (3) drying and finishing: the method sequentially comprises the steps of squeezing water, stretching, vacuum drying, hanging, airing, moisture regaining and vibration softening.
Example 2
The preparation method of the metal-free tanning antibacterial ecological leather at least comprises the following steps:
the step (a) of preparing a composite antibacterial agent comprises the following steps:
step one, stirring 12 parts of polyphosphoric acid, 35 parts of diethylene glycol dimethyl ether, 8 parts of thionyl chloride and 65 parts of phosphoric acid at 100 ℃ for 2 hours, and uniformly mixing to obtain a catalyst solution;
step two, taking 30 parts of catalyst solution, adding 65 parts of sulfate, stirring at 65 ℃ for 30 hours, uniformly mixing, then adding 130 parts of gluconic acid, uniformly mixing, adding 2 parts of polyphosphoric acid, reacting at 100 ℃ for 9 hours, adding 13 parts of gluconic acid, and heating to 180 ℃ for reacting for 0.8 hours. Cooling to 50 ℃, and adding 350 parts of water to obtain the gluco-pyrido-bisimidazole;
and step three, taking 100 parts of chitosan oligosaccharide, 40 parts of gluco-pyrido-pyridine bisimidazole, 350 parts of water, 5 parts of acetic acid and 10 parts of zinc chloride, uniformly mixing, then adding 18 parts of triethylamine, and reacting for 8 hours at 40 ℃ to obtain the zinc oxide-chitosan oligosaccharide/gluco-pyrido-pyridine bisimidazole composite antibacterial agent.
Step (b) is soft: 250% water, 1.5% multifunctional rewetting agent PELLAN GLH (Kai chemical company of Germany) and 0.2% nonionic degreasing agent Euscapon OC (Stta Co.) are added into the rotary drum, and the rotary drum is rotated for 30min at 48 ℃;
step (c) neutralization: adding 3.0% of synthetic tanning auxiliary Tamol X NL (Stoul company) into the bath, rotating for 60min, and regulating the pH of the bath to 4.0;
step (d) conventional water washing;
filling in the step (e): 50% water, 2.0% synthetic tanning auxiliary agent Tamol X NL (Stokes Co.), 3.0% silicon fatting agent Densmodrin CD (Stokes Co.), 3.5% polymer fatting agent Stahlite AL3 (Stokes Co.), 2.0% nonionic fatting agent AMIDOIL PLUS (Spanish Sha Bei Gongsi) are added to the drum, the temperature is 32 ℃, and the drum is rotated for 30min; adding 6.5% of sulfone synthetic tanning agent Tanicor SXP (Stokes corporation), 6.5% of sulfone-phenol copolymer synthetic tanning agent Basyntan MLB (Stokes corporation), 2.5% of dispersed tannin Tamol M (Stokes corporation), and rotating for 60min; the rotation is carried out for 150min by adding 3.0% of a silicon fatting agent Denscorin CD (Style company), 3.5% of a polymer fatting agent Stahlite AL3 (Style company), 2.0% of a nonionic fatting agent AMIDOIL PLUS (Spanish Sha Bei Gongsi), 3.5% of a sulfone synthetic tanning agent Tanicor SXP (Style company), 9.5% of a sulfone-phenol copolymer synthetic tanning agent Basyntan MLB (Style company), 2.5% of dispersed tannin Tamol M (Style company); adding 12.0% of composite synthetic tanning agent Basyntan X HL (Stokes company), 4.0% of acrylic polymer tanning agent TERGOTAN PMB (Stokes company) and 6.0% of melamine resin tanning agent RELUGAN DLF (Stokes company), and rotating for 60min;
and (f) fatting: adding 150% hot water at 60deg.C, 3.5% high concentration solvent oil AS-723 (Scoll company), 7.5% synthetic soft oil PELLASTOL 94S (Sema chemical company), and rotating at 52deg.C for 60min;
step (g) antibacterial: adding 6.0% zinc oxide-chitosan oligosaccharide/gluco-pyridine bisimidazole compound antibacterial agent into the bath liquid, rotating for 60min, adding 2.8% formic acid for 3 times, rotating for 30min each time, and regulating pH of the bath liquid to 3.4;
step (h) conventional water washing;
and (3) drying and finishing: the method sequentially comprises the steps of squeezing water, stretching, vacuum drying, hanging, airing, moisture regaining and vibration softening.
Example 3
The preparation method of the metal-free tanning antibacterial ecological leather at least comprises the following steps:
the step (a) of preparing a composite antibacterial agent comprises the following steps:
step one, stirring 15 parts of polyphosphoric acid, 40 parts of diethylene glycol dimethyl ether, 10 parts of thionyl chloride and 80 parts of phosphoric acid at 100 ℃ for 2 hours, and uniformly mixing to obtain a catalyst solution;
step two, taking 30 parts of catalyst solution, adding 80 parts of 2,3,5, 6-tetraminopyridine hydrochloride, stirring at 80 ℃ for 48 hours, uniformly mixing, then adding 160 parts of gluconic acid, adding 3 parts of polyphosphoric acid after uniformly mixing, reacting at 100 ℃ for 12 hours, adding 16 parts of gluconic acid, and heating to 180 ℃ for reacting for 1 hour. Cooling to 50 ℃, and adding 500 parts of water to obtain the gluco-pyrido-bisimidazole;
and step three, taking 100 parts of chitosan oligosaccharide, 50 parts of gluco-pyrido-pyridine bisimidazole, 500 parts of water, 5 parts of acetic acid and 10 parts of zinc chloride, uniformly mixing, then adding 20 parts of triethylamine, and reacting for 12 hours at 50 ℃ to obtain the zinc oxide-chitosan oligosaccharide/gluco-pyrido-pyridine bisimidazole composite antibacterial agent.
Step (b) is soft: adding 300% water, 3.0% multifunctional rewetting agent PELLAN GLH (Kai chemical company of Germany) and 0.3% nonionic degreasing agent Euscapon OC (Stta Co.) into the rotary drum, and rotating at 45deg.C for 30min;
step (c) neutralization: adding 5.0% of a synthetic tanning auxiliary Tamol X NL (Stoul company) into the bath, rotating for 60min, and regulating the pH of the bath to 4.3;
step (d) conventional water washing;
filling in the step (e): adding 80% water, 3.0% synthetic tanning auxiliary agent Tamol X NL (Stokes corporation), 5.0% silicon fatting agent Densmodrin CD (Stokes corporation), 6.0% polymer fatting agent Stahlite AL3 (Stokes corporation), 3.0% nonionic fatting agent AMIDOIL PLUS (Spanish Sha Bei Gongsi) into a rotary drum, and rotating for 30min at 35 ℃; adding 8.0% of sulfone synthetic tanning agent Tanicor SXP (Stokes corporation), 8.0% of sulfone-phenol copolymer synthetic tanning agent Basyntan MLB (Stokes corporation), 4.0% of dispersed tannin Tamol M (Stokes corporation), and rotating for 60min; the rotation is carried out for 150min by adding 5.0% of a silicon fatting agent Denscorin CD (Style company), 6.0% of a polymer fatting agent Stahlite AL3 (Style company), 3.0% of a nonionic fatting agent AMIDOIL PLUS (Spanish Sha Bei Gongsi), 5.0% of a sulfone synthetic tanning agent Tanicor SXP (Style company), 11.0% of a sulfone-phenol copolymer synthetic tanning agent Basyntan MLB (Style company), 4.0% of dispersed tannin Tamol M (Style company); 15.0% of a compound synthetic tanning agent Basyntan X HL (Stokes company), 6.0% of an acrylic polymer tanning agent TERGOTAN PMB (Stokes company) and 8.0% of a melamine resin tanning agent RELUGAN DLF (Stokes company) are added, and the mixture is rotated for 60 minutes;
and (f) fatting: 200% of hot water at 60 ℃ and 5.0% of high-concentration solvent grease AS-723 (Style company) and 10.0% of synthetic soft grease PELLASTOL 94S (Sema chemical company) are added into the bath liquid, and the bath liquid is rotated for 60min at 53 ℃;
step (g) antibacterial: adding 10.0% zinc oxide-chitosan oligosaccharide/gluco-pyridine bisimidazole compound antibacterial agent into the bath liquid, rotating for 60min, adding 3.0% formic acid for 3 times, rotating for 30min each time, and regulating pH of the bath liquid to 3.2;
step (h) conventional water washing;
and (3) drying and finishing: the method sequentially comprises the steps of squeezing water, stretching, vacuum drying, hanging, airing, moisture regaining and vibration softening.
Experimental test
The leathers obtained in examples 1, 2 and 3 were subjected to antibacterial test, and the results of examples 1, 2 and 3 were substantially the same as those shown in table 1 below: except that the free formaldehyde content of example 1 was 37.2mg/kg, the free formaldehyde content of example 2 was 44.7mg/kg, and the free formaldehyde content of example 3 was 38.6mg/kg.
TABLE 1 antibacterial ecological leather test results
The above description is illustrative of the embodiments using the present teachings, and is not intended to limit the scope of the present teachings to any particular modification or variation of the present teachings by those skilled in the art.
Claims (8)
1. The preparation method of the composite antibacterial agent is characterized by comprising the following steps of:
step (1): uniformly stirring and mixing 10-15 parts of polyphosphoric acid, 30-40 parts of diethylene glycol dimethyl ether, 5-10 parts of thionyl chloride and 50-80 parts of phosphoric acid at 90-110 ℃ to obtain a catalyst solution;
step (II): taking 25-35 parts of catalyst solution, adding 50-80 parts of salicide, stirring and mixing uniformly at 50-80 ℃, then adding 100-160 parts of gluconic acid, mixing uniformly, adding 1-3 parts of polyphosphoric acid, reacting for a period of time at 90-110 ℃, adding 10-16 parts of gluconic acid, heating to 175-185 ℃ for reacting for a period of time, cooling to 45-50 ℃, and adding 200-500 parts of water to obtain the bipyridyl bisimidazole gluconate;
step (III): mixing 95-105 parts of chitosan oligosaccharide, 30-50 parts of gluco-pyrido-pyridine bisimidazole, 200-500 parts of water, 5-10 parts of acetic acid and 10-15 parts of zinc chloride uniformly, then adding 15-20 parts of triethylamine, and reacting for a period of time at 30-50 ℃ to obtain a zinc oxide-chitosan oligosaccharide/gluco-pyrido-pyridine bisimidazole composite antibacterial agent;
the hydrochloride is 2,3,5, 6-tetraminopyridine hydrochloride or sulfate.
2. A composite antibacterial agent, characterized by being produced by the method of claim 1.
3. The preparation method of the metal-free tanning antibacterial ecological leather is characterized by at least comprising the following steps:
softening, neutralizing, washing, filling, fatting, sterilizing, washing, drying and finishing, and adding the zinc oxide-chitosan oligosaccharide/gluco-pyridine bisimidazole compound antibacterial agent prepared by the method of claim 1 into the antibacterial procedure.
4. The method for preparing the metal-free tanning antibacterial ecological leather according to claim 3, wherein the fatliquoring process and the filling process are carried out in the same bath, and the specific steps are as follows: adding 120-200% hot water, 2.0-5.0% high concentration solvent type grease, 5.0-10.0% synthetic soft grease into the bath liquid, and rotating at 50-53 ℃.
5. The method for preparing the metal-free tanning antibacterial ecological leather according to claim 3, wherein the antibacterial process and the filling and fatliquoring processes are carried out in the same bath, and comprises the following specific steps: adding 2-10% zinc oxide-chitosan oligosaccharide/glucodipyridyl bisimidazole compound antibacterial agent into the bath liquid, rotating, adding 2.5-3.0% formic acid for 3 times, rotating, and regulating pH of the bath liquid to 3.2-3.6.
6. The method for preparing the metal-free tanning antibacterial ecological leather according to claim 3, wherein the specific steps of the softening process are as follows: adding 200-300% water, 0.5-3.0% multifunctional rewetting agent and 0.1-0.3% nonionic degreasing agent into the rotary drum, and rotating at 45-53 ℃.
7. The method for preparing the metal-free tanning antibacterial ecological leather according to claim 3, wherein the neutralization process and the softening process are carried out in the same bath, and comprises the following specific steps: adding 1.0-5.0% synthetic tanning auxiliary agent into the bath liquid, rotating, and regulating pH of the bath liquid to 3.8-4.3.
8. The method for preparing the metal-free tanning antibacterial ecological leather according to claim 3, wherein the filling process comprises the following specific steps: adding 30-80% water, 1.0-3.0% synthetic tanning auxiliary agent, 1.5-5.0% silicon fatting agent, 1.5-6.0% polymer fatting agent and 1.5-3.0% nonionic fatting agent into a rotary drum, and rotating at 30-35 ℃; adding 5.0-8.0% sulfone synthetic tanning agent, 5.0-8.0% sulfone-phenol copolymer synthetic tanning agent, 1.0-4.0% dispersed tannin, and rotating; adding 1.5-5.0% of silicon fatliquoring agent, 1.5-6.0% of polymer fatliquoring agent, 1.5-3.0% of nonionic fatliquoring agent, 2.0-5.0% of sulfone synthetic tanning agent, 8.0-11.0% of sulfone-phenol copolymer synthetic tanning agent and 1.0-4.0% of dispersed tannin, and rotating; adding 8.0-15.0% of compound synthetic tanning agent, 2.0-6.0% of acrylic acid polymer tanning agent and 3.0-8.0% of melamine resin tanning agent, and rotating.
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